Co-polymerized acetylenic compositions

ABSTRACT

A composition is described comprising at least two co-crystallized acetylenic compounds, of different chemical structures, each containing at least one --C.tbd.C-C.tbd.C-- group and substituents selected from the group consisting of sulfonate, urethane and alcohol radicals, at least one of the compounds capable of undergoing a contrasting color change upon exposure to actinic radiation or thermal annealing, wherein the composition exhibits a substantially different thermogram than the sum of thermograms of the individual components as obtained by differential scanning calorimetry. 
     A device is also described useful for measuring the time-temperature or radiation-dosage history of an article comprising a substrate having deposited thereon the described composition. 
     A process is also described for producing the composition of this invention.

This application is a divisional of co-pending parent application, Ser.No. 817,069, filed July 19, 1977, and related to co-pending applicationSer. No. 960,507, filed Nov. 13, 1978, also of the above-referencedparent application.

CROSS-REFERENCE TO RELATED APPLICATIONS

The subject matter of this application was disclosed but not claimed ina prior application, U.S. patent application 660,562, filed Feb. 23,1976 by the present inventor and others, which issued as U.S. Pat. No.3,999,946 on Dec. 28, 1976.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel co-crystallized compositions comprisingat least two acetylenic compounds, useful in measuring thetime-temperature or radiation-dosage history of an article.

2. Brief Description of the Prior Art

Radiation sensitive compositions containing a polyacetylenic compound,having a minimum of two conjugated acetylenic linkages, commingled withan organic pi-acid electron acceptor are described in U.S. Pat. No.3,501,308 (Adelman, 1970). However, compositions comprising at least twoacetylenic compounds, each containing at least one --C.tbd.C--C.tbd.C--group, are not described by the reference.

Image-receptive elements containing fixed position photosensitivecrystals of polyacetylenic compounds, having at least two acetyleniclinkages in a conjugated system, are described in U.S. Pat. No.3,501,297 (Creamens, 1970). Reference is made to a mixture of11,13-tetracosadiynedioic acid containing up to about 20 to 30 percentof monoethyl ester of 11,13-tetracosadiynedioic acid useful in animage-receptive element, but no properties are described to suggest thatthe compounds in the composition are co-crystallized compounds ratherthan being a simple mixture.

Acetylenic compounds having at least two conjugated C.tbd.C groups havebeen disclosed as time-temperature history indicators in U.S. Pat. No.3,999,946. Monomeric acetylenic compounds, of the formula,R--C.tbd.C.tbd.C--R, where R is a monovalent radical, are colorless andare polymerizable in the solid state, either thermally or by actinicradiation. As the polymerization proceeds, these compounds undergo acontrasting color change to blue or pink and the color intensifies withtime until the compounds finally develop into metallic-looking polymers.Thus, the compounds can be used as time-temperature history indicatorsand as radiation-dosage indicators. The reference also describespolymers of the type [C.tbd.C--(CH₂)_(m) OCONH(CH₂)₆ NHOCO(CH₂)_(m)--C.tbd.C]_(n) where m is 2, 3 or 4 and n is large, wherein a polymercontaining polymeric repeating units of the same empirical formula,undergo color changes upon thermal annealing.

SUMMARY OF THE INVENTION

It has been unexpectedly found that by dissolving in a solvent two ormore acetylenic compounds, of different chemical structures, eachcontaining at least one --C.tbd.C--C.tbd.C-- group, and either removingthe solvent therefrom at such rate that it exceeds the rate ofinitiating crystallization of each acetylenic compound separately, ormixing the solution with a liquid which is miscible with the solvent butacts as a nonsolvent for the co-crystallized composition, at such ratethat mixing is complete before the initiation time for crystallizationof each acetylenic compound separately from the same solvent mixture, aco-crystallized composition of the two acetylenic compounds is obtainedin which the thermogram of the composition is different from the sum ofthe thermograms of the individual components as measured by differentialscanning calorimetry. The obtained co-crystallized compositions exhibitsurprisingly different reactivity rates of color change upon exposure toactinic radiation or thermal annealing than the individual components.Thus, the applicable range of utility of acetylenic compounds can beextensively varied for use in measuring the time-temperature orradiation-dosage history of an article.

In accordance with this invention, there is provided a compositioncomprising at least two co-crystallized acetylenic compounds, ofdifferent chemical structures, each containing at least one--C.tbd.C--C.tbd.C-- group and substituents selected from the groupconsisting of sulfonate, urethane and alcohol radicals, at least one ofthe compounds capable of undergoing a contrasting color change uponexposure to actinic radiation or thermal annealing, wherein thecomposition exhibits a substantially different thermogram than the sumof the thermograms of the individual components as obtained bydifferential scanning calorimetry.

A device is also provided useful for measuring the time-temperature orradiation-dosage history of an article comprising a substrate havingdeposited thereon at least one of the compositions of the invention.

Further provided is a device for measuring temperature comprising asubstrate having deposited thereon at least one thermochromicco-crystallized composition.

A process for making the compositions of this invention is also providedwhich comprises the steps of

(a) dissolving at least two acetylenic compounds in a solvent therefor,thereby forming a solution; and

(b) recovering the co-crystallized composition from the solution byremoval of the solvent at such rate that it exceeds the rate ofinitiating crystallization of each acetylenic compound separately.

Another process for making the compositions of this invention is alsoprovided which comprises the steps of

(a) dissolving at least two acetylenic compounds in a solvent therefor,thereby forming a solution;

(b) mixing the solution with a liquid, which is miscible with thesolvent but is non-solvent for the co-crystallized composition, at suchrate that mixing is complete before the initiation time forcrystallization of each acetylenic compound separately from the samesolvent mixture.

Another process is provided for making the compositions of thisinvention directly in a solvent which comprises the steps of

(a) reacting one or more acetylenic diols with one or more isocyanatesor organic sulfonic acid agents, such that the total of different diolsand isocyanates or organic sulfonic agents is at least three; and

(b) recovering the co-crystallized composition from the solution.

Further provided is a process for making the compositions of theinvention which comprises the steps of (a) vaporizing at least twoacetylenic compounds and (b) depositing the resulting vapor onto asubstrate.

There is also provided a process for making the compositions of thisinvention which comprises the steps of (a) forming a melt of at leasttwo acetylenic compounds and (b) cooling the melt rapidly.

Also provided is a copolymeric composition comprising an irradiated orthermally annealed product of a composition comprised of at least twoco-crystallized acetylenic compounds, of different chemical structures,each containing at least one --C.tbd.C--C.tbd.C-- group and substituentsselected from the group consisting of sulfonate, urethane, and alcoholradicals, at least one of the compounds capable of undergoing acontrasting color change upon exposure to actinic radiation or thermalannealing, wherein the composition exhibits a substantially differentthermogram than the sum of thermograms of the individual components asobtained by differential scanning calorimetry.

Further provided is a shaped article produced from the above copolymericcomposition which possesses a decomposition temperature of at leastabout 20° C. above its melting point.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates thermograms, obtained by differential scanningcalorimetry, of 3,5-octadiyn-1,8-diol (ODD) and 4,6-decadiyn-1,10-diol(DDD) as pure materials, individually, and, as co-crystallizedcompositions and simple mixtures thereof containing 20, 40, 60 and 80weight percent of each component.

FIG. 2 illustrates thermograms, obtained by differential scanningcalorimetry, of 2,4-hexadiyn-1,6-diol bis(n-butylurethane) (HDDBU) and2,4-hexadiyn-1,6-diol bis(ethylurethane) (HDDEU), individually as purematerials and as co-crystallized compositions and simple mixturesthereof containing 20, 40, 60 and 80 weight percent of each component.

FIG. 3 illustrates a plot of reciprocal time in hours (ordinate) versusthe initial concentration in the composition, prior to thermalannealing, of 2,4-hexadiyn-1,6-diol bis(bromophenylurethane) (HDDPBPU)as weight percent in co-crystallized compositions of HDDPBPU and2,4-hexadiyn-1,6-diol bisphenylurethane (HDDPU) indicating therelationship of time required for the co-crystallized composition toturn metallic green or rusty red (end point color) by thermal annealingat 80° C., as a function of the concentration of HDDPBPU in theco-crystallized composition. The extrapolated portion of the curvebetween 10 and 20 weight percent concentration of HDDPBPU is anapproximate fit of the experimental points from FIG. 4 and representsthe region of optimum thermal reactivity of these co-crystallizedcompositions.

FIG. 4 is a sequential array illustrating the differences in reactivityof color change, during thermal annealing at 80° C. for differentexposure times, of a series of co-crystallized compositions of HDDPU andHDDPBPU containing varying weight concentrations of HDDPU. Theindividual squares are comprised of filter paper coated with thedesignated composition and which were individually thermally annealedfor the indicated times at 80° C. The squares were then assembled toform a sequential array and were visually inspected by comparingdeveloped colors of each square with others in the array and assigned acomparative number corresponding to the developed color as listed in thecomparative Color Table. Proceeding vertically upward in each column,which represents one specific composition, the first square to read 7,designating the end-point color, represents the time variable used asthe experimental point to form the curve in FIG. 3.

DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

We have unexpectedly found that the thermal and radiation reactivity ofacetylenic compounds containing at least one --C.tbd.C--C.tbd.C-- groupcan be successfully altered by co-crystallizing two or more of thecompounds, having different chemical structures, wherein the producedco-crystallized acetylenic compounds have either unexpectedly higher orlower reactivity upon exposure to actinic radiation or thermal annealingthan the individual compounds. The term "actinic radiation" refers toultraviolet radiation, gama radiation, electron beam and the like whichis of sufficiently high energy to cause chemical changes, i.e.polymerization by 1,4-addition between the acetylenic compounds. Theterm "thermal annealing" refers to heating at sufficient temperature, asby infrared radiation, flame, laser-beam, microwave radiation and thelike which is sufficiently high energy to cause chemical changes, i.e.polymerization by 1,4-addition between the acetylenic compounds. By theterm "co-crystallized" as used herein is meant a crystalline compositioncontaining at least two different components in its crystalline lattice,wherein the new crystalline lattice exhibits different thermalproperties and is distinguishable from the crystalline lattices of theindividual components.

The co-crystallized compositions of acetylenic compounds of thisinvention are distinguishable and unique with respect to simple mixturesof the individual components in that the co-crystallized compositionexhibits a substantially different thermogram than the sum of thethermograms of the individual components as measured by differentialscanning calorimetry. This technique measures changes in enthalpy withrespect to temperature over a broad temperature range and indicatesmelting behavior, phase changes and temperature of transitions. Thethermogram of a simple mixture will, in general, exhibit the sum of thethermal behavior of the two components, whereas the co-crystallizedcomposition will exhibit a substantially different thermogram.

By the term "substantially different thermogram" is meant that thethermogram of the co-crystallized composition will not be identical withrespect to both the overall profile of endotherms and exotherms and thetemperatures at which the endotherms and exotherms occur as contrastedto the thermogram of a simple mixture of the components. The differenceswill be readily distinguishable in that the thermogram of theco-crystallized composition will usually consist of one peak value whilethat of the simple mixture will usually consist of at least two distinctpeak values, each corresponding to the peak value of each individualcomponent. The thermogram of the co-crystallized composition will vary,depending upon the concentration of each of the components in thecomposition, wherein each component acetylenic compound is present in atleast about 0.1 percent by weight of the composition. For example, an80/20 composition by weight of 3,5-octadiyn-1,8-diol (ODD) and4,6-decadiyn-1,10-diol (DDD) yields a single peak in the thermogram,whereas a 60/40 composition by weight of the same components yields astraight line, indicating the composition is amorphous and does notdisplay crystalline characteristics in the temperature range usuallymeasured, e.g. -100° C. to 200° C.

Since the co-crystallized composition exhibits a different thermogram,its crystalline properties are different from those of a simple mixtureresulting in either greater or lesser polymerization reactivity andsubsequently rate of color change upon exposure to actinic radiation orthermal annealing; whereas the simple mixture will exhibit propertieswhich are merely an additive combination of the individual componentsdepending upon the proportions of each component present. For example, aco-crystallized composition containing 12 weight percent2,4-hexadiyn-1,6-diol bis(pchlorophenylurethane) (HDDPCPU)/88 weightpercent 2,4-hexadiyn-1,6-diol bisphenylurethane (HDDPU) exhibits anincreased polymerization rate of about 700 times faster than that of asimple mixture of the two or 2,4-hexadiyn-1,6-diol bis(phenylurethane),alone.

Conversely, a co-crystallized composition of 2,4-hexadiyn-1,6-diolbis(p-toluenesulfonate) (HDDPTS) and 3,5-octadiyn-1,8-diolbis(p-toluenesulfonate) (ODDPTS) exhibits a decreased reactivity towardpolymerization by thermal annealing as contrasted to a simple mixture ofthe two.

This general altered reactivity of a co-crystallized composition isthought to be due to changes in the packing of the molecules in thesolid state. Alteration of the crystallographic packing by theintroduction of other closely related acetylenic molecules probablyaffects the activation energy or the kinetics of the polymerizationprocess in an unexpected manner. Generally, the best results areobtained for achieving efficient crystallographic packing of theacetylenic molecules in the solid state if the molecules chosen havesimilar chemical structure. The thermal or radiation response whichgives rise to the color changes of the co-crystallized compositionusually corresponds to addition reactions which transform the conjugatedacetylenic functionalities in the composition to fully conjugated chainsof the type (═C--C.tbd.C--C═)_(q), where q corresponds to the number ofmutually reacting acetylenic functionalities, which is dependent uponreaction conditions. The intense coloration of the polymerizedcompositions results from the fully conjugated chains.

The acetylenic compounds in the co-crystallized composition are ofdifferent chemical structures. Being different chemical structures, theymay have the same empirical formulas, e.g. a composition comprised ofthe bis(p-chlorophenylurethane) and bis(o-chlorophenylurethane) of2,4-hexadiyn-1,6-diol. However, the term "different chemical structures"does not include different molecular weight fractions of a polymer, suchas

    --[C.tbd.C--(CH.sub.2).sub.2 OCONH(CH.sub.2).sub.6 NHOCO--(CH.sub.2).sub.2 --C.tbd.C].sub.n

where different values of n would give rise to different physicalstructures, having the same empirical formula, but not differentchemical structures.

In general, any two acetylenic compounds, of different chemicalstructures, each containing at least one --C.tbd.C--C.tbd.C-- group andsubstituents selected from the group consisting of sulfonate, urethaneand alcohol radicals, wherein at least one of the acetylenic compoundsis capable of undergoing a contrasting color change upon exposure toactinic radiation or thermal annealing, may be used to form thecompositions of this invention.

Included among the suitable acetylenic compounds of the invention arediynes, triynes, tetraynes and hexaynes of the general formulasdescribed in U.S. Pat. No. 3,999,946, wherein the acetylenic compoundscontain substituents selected from the group consisting of sulfonate,urethane and alcohol radicals, wherein the substituents can be the sameor different, and if different, result in an asymmetrically substitutedacetylenic compound.

It is preferred in the invention to use the acetylenic compounds whichare diynes and it is particularly preferred to use diynes selected fromthe group consisting of 2,4-hexadiyn-1,6-diol, 3,5-octadiyn-1,8-diol,4,6-decadiyn-1,10-diol, 5,7-dodecadiyn-1,12-diol and urethane andsulfonate derivatives thereof.

Preferred urethane substituents include those of the formula RNHOCO-wherein R is C₁ -C₁₈ alkyl, designated as containing 1 to 18 carbonatoms, and being linear or branched; C₁ -C₁₄ alkoxycarbonylmethyl, thatis, the alkyl portion of the radical containing 1 to 14 carbon atoms,and being linear or branched; phenyl; halophenyl, containing at leastone halogen, such as fluorine, chlorine, bromine and iodine or mixturesthereof in the o, m and p-positions of the phenyl ring; C₁ -C₁₄alkylphenyl, designated as containing an alkyl group of 1 to 4 carbonsbeing linear or branched, in the o, m, or p-positions of the phenylring; and C₁ -C₄ alkoxyphenyl, that is, the alkyl portion of the radicalcontaining 1 to 4 carbon atoms being either linear or branched in the o,m, or p-positions of the phenyl ring.

Representative examples of urethane substituents include those where Ris methyl, ethyl, isopropyl, t-butyl, n-dodecyl and n-octadecyl;methoxy-, ethoxy-, isopropoxy-, t-butoxy-, n-dodecyloxy- andn-tetradecyloxycarbonylmethyl; p-chloro-, o-bromo-, m-iodo-,2,4-dichloro-, 3,5-dibromo-, p-fluoro-, and 2-chloro-3-bromophenyl;o-tolyl-, m-tolyl-, p-tolyl-, 4-ethyl-, 4-isopropyl-, 3-n-butyl- and4-t-butylphenyl; p-methoxy-, o-ethoxy-, m-isopropoxy-, andp-t-butoxyphenyl.

Preferred sulfonate substituents include those of the formula ZSO₂ O-wherein Z is C₁ -C₁₈ alkyl, designated as containing 1 to 18 carbonatoms being linear or branched; phenyl; halophenyl, containing at leastone halogen, such as fluorine, chlorine, bromine and iodine or mixturesthereof in the o, m or p-positions of the phenyl ring; C₁ -C₄alkylphenyl, designated as containing an alkyl group of 1 to 4 carbonatoms being linear or branched in the o, m or p-positions of the phenylring.

Representatives examples of sulfonate substituents include those where Zis methyl, ethyl, isopropyl, t-butyl, n-dodecyl and n-octadecyl;p-chloro-, o-bromo-, m-iodo-, 2,4-dichloro-, 3,5-dibromo-, p-fluoro-,and 2-chloro-3-bromophenyl; o-tolyl, m-tolyl, p-tolyl, 4-decylphenyl,4-isopropylphenyl, 3-n-butylphenyl and 4-t-butylphenyl.

Examples of specific acetylenic compounds useful in the practice of theinvention include:

A. Sulfonates

1. p-CH₃ -C₆ H₄ SO₃ CH₂ --C.tbd.C--C.tbd.C--CH₂ SO₃ C₆ H₄ --p--CH₃2,4-hexadiyn-1,6-diol bis(p-toluenesulfonate)

2. p--CH₃ --C₆ H₄ SO₃ --(CH₂)₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --SO₃ --C₆ H₄--p--CH₃ 3,5-octadiyn-1,8-diol bis(p-toluenesulfonate)

3. p--CH₃ --C₆ H₄ SO₃ CH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C CH2,4,8-nonatriyn-1-ol p-toluene sulfonate

4. [p--CH₃ --C₆ H₄ SO₃ CH₂ C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.C--]₂2,4,8,10,14,16-octadecahexayn-1,18-diol bis(p-toluenesulfonate)

B. Urethanes

1. C₆ H₅ NHOCOCH₂ --C.tbd.C--C.tbd.C--CH₂ OCONHC₆ H₅2,4-hexadiyn--1,6-diol bis(phenylurethane)

2. C₂ H₅ NHOCOCH₂ --C.tbd.C--C.tbd.C--CH₂ OCONHC₂ H₅2,4-hexadiyn--1,6-diol bis(ethylurethane)

3. C₄ H₉ NHOCOCH₂ --C.tbd.C--C.tbd.C--CH₂ OCONHC₄ H₉2,4-hexadiyn--1,6-diol bis(n-butylurethane)

4. p--Cl--C₆ H₄ --NHOCOCH₂ --C.tbd.C--C.tbd.C--CH₂ OCONHC₆ H₄ --p--Cl2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)

5. p--Br--C₆ H₄ --NHOCOCH₂ --C.tbd.C--C.tbd.C--CH₂ OCONHC₆ H₄ --p--Br2,4-hexadiyn-1,6-diol bis(p-bromophenylurethane)

6. C₆ H₅ (CH₂)₂ C.tbd.C--C.tbd.C--CH₂ OCONHC₂ H₅7-phenyl-2,4-heptadiyn-1-ol-ethylurethane

7. C₂ H₅ NHOCO(CH₂)₂ --C.tbd.C--C.tbd.C--(CH₂)₂ OCONHC₂ H₅3,5-octadiyn-1,8-diol bis(ethylurethane)

8. CH₃ NHOCO(CH₂)₄ --C.tbd.C--C.tbd.C--(CH₂)₄ OCONHCH₃5,7-dodecadiyn-1,12-diol bis(methylurethane)

9. C₆ H₅ NHOCO(CH₂)₄ --C.tbd.C--C.tbd.C--(CH₂)₄ OCONHC₆ H₅5,7-dodecadiyn-1,12-diol bis(phenylurethane)

10. CH₃ NHOCOCH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.CH2,4,8-nonatriyn-1-ol-methylurethane

11. C₂ H₅ NHOCOCH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.CH2,4,8-nonatriyn-1-ol-ethylurethane

12. C₂ H₅ NHOCOCH₂ --C.tbd.C--C.tbd.C--C.tbd.C--C.tbd.C--CH₂ OCONHC₂ H₅2,4,6,8-decatetrayn-1,10-diol bis(ethylurethane)

13. CH₃ NHOCO--CH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.C--C.tbd.C--CH₂--OCONHCH₃ 2,4,8,10-dodecatetrayn-1,12-diol bis(methylurethane)

14. C₂ H₅ NHOCOCH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.C--C.tbd.C--CH₂OCONHC₂ H₅ 2,4,8,10-dodecatetrayn-1,12-diol bis(ethylurethane)

15. C₆ H₅ NHOCOCH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.C--C.tbd.C--CH₂OCONHC₆ H₅ 2,4,8,10-dodecatetrayn-1,12-diol bis(phenylurethane)

16. [CH₃ NHOCOCH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.C--]₂2,4,8,10,14,16-octadecahexayn-1,18-diol bis(methylurethane)

17. [C₂ H₅ NHOCOCH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.C--]₂2,4,8,10,14,16-octadecahexayn-1,18-diol bis(ethylurethane)

18. [C₆ H₅ NHOCOCH₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --C.tbd.C--]₂2,4,8,10,14,16-octadecahexayn-1,18-diol bis(phenylurethane)

C. Alcohols

1. HO-(CH₂)₂ --C.tbd.C--C.tbd.C--(CH₂)₂ --OH 3,5-octadiyn-1,8-diol

2. HO-(CH₂)₃ --C.tbd.C--C.tbd.C--(CH₂)₃ -OH 4,6-decadiyn-1,10-diol

3. HOOC(CH₂)₈ --C.tbd.C--C.tbd.C--CH₂ OH 10,12-tetradecadiynoicacid-14-ol

Similarly suitable for the practice of the invention are cycliccompositions such as ##STR1## where R is -CO(CH₂)₃ CO--, --CO(CH₂)₄CO--, --(CH₂)₃ --, --CH₂ CH═CHCH₂ -- (cis or trans), --CH₂ C.tbd.CCH₂ --or --CH₂ (m--C₆ H₄)CH₂ -.

In general, any of the acetylenic compounds included in the inventioncan be mutually co-crystallized to form a co-crystallized composition.More than two acetylenic compounds can be employed with the provisosthat at least one acetylenic compound undergoes a contrasting colorchange upon exposure to actinic radiation or thermal annealing, and eachcomponent is present in at least about 0.1 weight percent of theco-crystallized composition.

Representative examples of suitable co-crystallized compositions includethe following:

Co-Crystallized Compositions

2,4-hexadiyn-1,6-diol bisphenylurethane and

2,4-hexadiyn-1,6-diol bis(p-bromophenylurethane)

2,4-hexadiyn-1,6-diol bisphenylurethane and

2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)

3,5-octadiyn-1,8-diol

4,6-decadiyn-1,10-diol

2,4-hexadiyn-1,6-diol bis(n-butylurethane)

plus 2,4-hexadiyn-1,6-diol (bis(ethylurethane)

2,4-hexadiyn-1,6-diol bis(p-bromophenylurethane)

and 2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)

plus 2,4-hexadiyn-1,6-diol bis(o-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(o-tolylurethane) plus

2,4-hexadiyn-1,6-diol bis(m-tolylurethane)

2,4-hexadiyn-1,6-diol bis(n-hexylurethane) plus

2,4-hexadiyn-1,6-diol bis(m-butylurethane)

2,4-hexadiyn-1,6-diol bis(m-tolylurethane) plus

2,4-hexadiyn-1,6-diol bis(p-tolylurethane)

2,4-hexadiyn-1,6-diol bis(o-tolylurethane) plus

2,4-hexadiyn-1,6-diol bis(p-tolylurethane)

2,4-hexadiyn-1,6-diol bis(m-chlorophenylurethane)

plus 2,4-hexadiyn-1,6-diol bis(o-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(p-tolylurethane) plus

2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(p-methoxyphenylurethane)

plus 2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(phenylurethane) plus

2,4-hexadiyn-1,6-diol bis(m-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(phenylurethane) plus

2,4-hexadiyn-1,6-diol bis(p-methoxyphenylurethane)

2,4-hexadiyn-1,6-diol bis(phenylurethane) plus

2,4-hexadiyn-1,6-diol bis(p-ethoxyphenylurethane)

2,4-hexadiyn-1,6-diol bis(phenylurethane) plus

2,4-hexadiyn-1,6-diol bis(o-chlorophenylurethane)

3,5-octadiyn-1,8-diol bis(p-chlorophenylurethane)

plus 3,5-octadiyn-1,8-diol bis(m-chlorophenylurethane)

3,5-octadiyn-1,8-diol bis(m-tolylurethane) plus

3,5-octadiyn-1,8-diol bis(o-tolylurethane)

4,6-decadiyn-1,10-diol bis(n-butoxycarbonylmethylurethane) plus4,6-decadiyn-1,10-diol bis(ethoxycarbonylmethylurethane)

Co-Crystallized Compositions (continued)

5,7-dodecadiyn-1,12-diol bis(o-tolylurethane)

plus 5,7-dodecadiyn-1,12-diol bis(m-tolylurethane)

5,7-dodecadiyn-1,12-diol bis(p-chlorophenylurethane)

plus 5,7-dodecadiyn-1,12-diol bis(p-bromophenylurethane)

2,4-hexadiyn-1,16-diol bis(p-ethoxyphenylurethane) plus

3,5-octadiyn-1,8-diol bis(p-ethoxyphenylurethane)

2,4-hexadiyn-1,6-diol bis(m-tolylurethane) plus

3,5-octadiyn-1,8-diol bis(m-tolylurethane)

2,4-hexadiyn-1,6-diol bis(n-hexylurethane) plus

3,5-octadiyn-1,8-diol bis(n-hexylurethane)

2,4-hexadiyn-1,6-diol bis(m-chlorophenylurethane)

plus 3,5-octadiyn-1,8-diol bis(m-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(n-butylurethane) plus

5,7-dodecadiyn-1,12-diol bis(n-butylurethane)

4,6-decadiyn-1,10-diol bis(n-butylurethane) plus

5,7-dodecadiyn-1,12-diol bis(n-butylurethane)

3,5-octadiyn-1,8-diol plus 4,6-decadiyn-1,10-diol

2,4-hexadiyn-1,6-diol bis(p-ethoxyphenylurethane)

plus 2,4-hexadiyn-1,6-diol bis(phenylurethane)

2,4-hexadiyn-1,6-diol bis(p-tolylurethane) plus

2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(p-methoxyphenylurethane)

plus 2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)

2,4-hexadiyn-1,6-diol bis(o-chlorophenyl)urethane

plus 2,4-hexadiyn-1,6-diol bisphenylurethane

Preferred co-crystallized compositions are: 2,4-hexadiyn-1,6-diolbis(phenylurethane) and 2,4-hexadiyn-1,6-diolbis(p-bromophenylurethane); 2,4-hexadiyn-1,6-diol bis(phenylurethane)and 2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane);2,4-hexadiyn-1,6-diol bis(n-butylurethane) and 2,4-hexadiyn-1,6-diolbis(ethylurethane); 2,4-hexadiyn-1,6-diol bis(p-toluenesulfonate) and3,5-octadiyn-1,8-diol bis(p-toluenesulfonate); and 3,5-octadiyn-1,8-dioland 4,6-decadiyn-1,10-diol.

Particularly preferred are the compositions containing2,4-hexadiyn-1,6-diol bis(phenylurethane) and 2,4-hexadiyn-1,6-diolbis(p-chlorophenylurethane) or 2,4-hexadiyn-1,6-diolbis(p-bromophenylurethane) wherein each of the latter two components arepresent from about 0.1 to about 30 weight percent of the composition.

In general, the co-crystallized composition of this invention willgradually undergo a color change, upon thermal annealing or exposure toactinic radiation, from colorless to a red color and finally to a darkmetallic color. In certain instances, the color change may be other thanthrough a gradual red transition, for example, a blue transition, andthe final color may be a dark blue but not necessarily metallic.However, in either event, the co-crystallized composition is useful inthe applications described herein.

Certain co-crystallized compositions are unexpectedly thermochromic;that is, upon thermal annealing or exposure to actinic radiation theygradually form a dark or metallic color and then upon further thermalannealing they turn deep red, but in a reversible fashion, over a narrowrange of temperature. If coated on the surface of an article or suitablesubstrate, these thermochromic compositions will exhibit this reversiblecontrasting color change when a definite temperature is reached and thuscan be used to indicate a specific temperature. The temperature of thereversible color transition can be varied by suitable adjustment of theproportions of the individual acetylenic compounds producing differentco-crystallized compositions which can be used to cover a wide range oftemperatures just like a thermometer.

Examples of co-crystallized compositions which are thermochromic are4,6-decadiyn-1,10-diol bis(ethoxycarbonylmethylurethane) and4,6-decadiyn-1,10-diol bis(n-butoxycarbonylmethylurethane); and4,6-decadiyn-1,10-diol bis(ethoxycarbonylmethylurethane) and5,7-dodecadiyn-1,12-diol bis(ethoxycarbonylmethylurethane).

Certain co-crystallized compositions exhibit a novel property in thatthe thermal reactivity, i.e. the rate of color development upon thermalannealing, is greater than any of the component acetylenic compounds.For example, co-crystallized compositions of HDDPU,2,4-hexadiyn-1,6-diol bis (phenylurethane) and HDDPCPU,2,4-hexadiyn-1,6-diol bis (p-chlorophenylurethane); and, HDDPU andHDDPBPU, 2,4-hexadiyn-1,6-diol bis(p-bromophenylurethane) exhibitthermal reactivity rates which are greater by a factor of at least abouttwo and usually above ten, than either of the reactivities of theindividual acetylenic compounds. FIG. 3 illustrates that the thermalreactivity of HDDPU/HDDPBPU co-crystallized compositions are greaterthan the thermal reactivity of HDDPU, which has about the same thermalreactivity as HDDPBPU. Co-crystallized compositions which exhibit agreater thermal reactivity than any of the component acetyleniccompounds are also a subject of this invention and includeco-crystallized compositions of HDDPU/HDDPCPU; HDDPU/HDDPBPU; and HDDEU,2,4-hexadiyn-1,6-diol bis (ethylurethane)/HDDBU, 2,4-hexadiyn-1,6-diolbis(n-butylurethane).

Five processes for making the co-crystallized compositions of theinvention from the acetylenic compounds described herein are alsosubjects of this invention. The first process comprises the steps of (a)dissolving at least two acetylenic compounds in a solvent therefore,thereby forming a solution; (b) recovering the co-crystallizedcomposition from the solution by removal of the solvent at such ratethat it exceeds the rate of initiating crystallization of eachacetylenic compound separately.

The fast rate of removal of the solvent can be accomplished bydistillation of the solvent under reduced pressure or by rapid spraydrying of the solution. In either modification, the solvent is removedat a faster rate than the rate of initiating crystallization of eachacetylenic compound separately, which thereby results in aco-crystallized composition since now the acetylenic compounds willuniformly co-crystallize out of the solution at the same rate. It ispreferred to use spray drying as the technique for evaporating thesolvent since it doesn't require the use of bulky vacuum distillationequipment.

One modification of this process is to deposit the solution as by spraydrying directly onto a substrate in step (a) of the above process,thereby resulting in a co-crystallized composition being directlyapplied to a substrate for use as a time-temperature or radiation-dosageindicator.

Suitable solvents for the process include alkyl esters of monocarboxylicacids, higher alkyl alcohols containing more than one carbon atom,alkylated benzenes, cyclic ethers, alkyl ketones, alkyl glycol ethers,halogenated alkyl hydrocarbons and the like. Representative examplesinclude ethyl acetate, methyl propionate, ethanol, butanol, isopropanol,toluene, xylene, trimethylbenzene, isopropylether, 1,2-dimethoxyethane,tetrahydrofuran, dioxane, acetone, ethylmethyl ketone, chloroform,dichloromethane and mixtures thereof. Especially preferred as solventsare 1,2-dimethoxyethane, dioxane, tetrahydrofuran, acetone, chloroform,ethanol, xylene and ethyl acetate. The process may be conducted, forexample, at room temperature by rapid evaporation of solutionscontaining from about 0.0001 to 5.0 parts, and preferably about 0.002 to0.2, parts by weight of combined acetylenic compounds per part by weightof solvent or solvent blend.

The second process comprises the steps of (a) dissolving at least twoacetylenic compounds in a solvent therefor, thereby forming a solution;(b) mixing the solution with a liquid, which is miscible with thesolvent, but is a non-solvent for the co-crystallized composition, atsuch rate that mixing is complete before the initiation time forcrystallization of each acetylenic compound separately from the samesolvent mixture.

The solvents which are applicable in this process are the same as thosediscussed above.

Suitable liquids which are miscible with the solution solvent but act asa non-solvent for the composition include paraffins, such as hexane andheptane, lower alkyl ethers containing 2 to 4 carbon atoms, such asdiethyl ether, water, methanol and benzene.

The weight ratio of solvent to total weight of acetylenic compounds isthe same as described above and generally the weight ratio of liquid tosolvent is about 1 to 10 parts of liquid per part of solvent and it ispreferred to use about 5 parts of liquid per part of solvent.

Mixing can be accomplished by either adding the solution of acetyleniccompounds to the liquid or by vice versa. However, it is preferred toadd the solution to the liquid with adequate stirring to insure completeconversion of the acetylenic compounds to a co-crystallized composition.In general, mixing is carried out at ambient temperature.

The third process comprises synthesizing the co-crystallizedcompositions directly in the solvent which comprises the steps of: (a)reacting one or more acetylenic diols with one or more isocyanates ororganic sulfonyl acid agents, such that the total of different diols andisocyanates or organic sulfonic acid agents is at least three; and (b)recovering the co-crystallized composition from the solution.

The solvents useful in this process are the same as described above.

The acetylenic diols, isocyanates and organic sulfonic acid reagentssuitable in the process are adequately described both in U.S. Pat. No.3,999,946 and in the above discussion, where the isocyanates contain Rradicals including those discussed previously and the organic sulfonicacid agents contain Z radicals including those discussed previously. Theacetylenic diols, isocyanates and organic sulfonic acid reagents andcombinations thereof will become obvious to one skilled in the art froma reading of the above patent and the above disclosure contained herein.

The limitation in this process is that the total number of diols andisocyanates or diols and organic sulfonic acid agents is at least three,thereby resulting in a co-crystallized composition directly recoverablefrom the reaction mixture. For example, methylisocyanate can be reactedwith a mixture of 2,4-hexadiyn-1,6-diol and 3,5-octadiyne-1,8-diol toyield a co-crystallized composition of (1) 2,4-hexadiyn-1,6-diolbis(methylurethane) and (2) 3,5-octadiyn-1,8-diol bis(methylurethane).Similarly, methylisocyanate and ethylisocyanate can be reacted with2,4-hexadiyn-1,6-diol to yield a co-crystallized composition of (1)2,4-hexadiyn-1,6-diol bis(methylurethane), (2) 2,4-hexadiyn-1,6-diolbis(ethylurethane) and (3)2,4-hexadiyn-1-ol-methylurethane-6-ol-ethylurethane.

It is preferred in the process to react one acetylenic diol with atleast two isocyanates or at least two organic sulfonic acid agents.

The fourth process for preparing co-crystallized compositions of thisinvention comprises (a) forming a melt of at least two acetyleniccompounds and (b) cooling the melt rapidly.

In general, two or more acetylenic compounds are mixed and heated abovetheir melting points, or until a melt is formed and upon rapidly coolinga co-crystallized composition is obtained. By the term "rapid cooling"is meant cooling at a faster rate than the rate of initiatingcrystallization of each acetylenic compound separately. Deposition of amixture of acetylenic compounds from solution resulting in a finelydivided mixture, followed by heating until a melt is formed, thenrapidly cooling, is a preferred method of obtaining a co-crystallizedcomposition from the melt. For example, the co-crystallized compositionsof ODD/DDD, whose thermograms are illustrated in FIG. 1, were preparedby deposition of a mixture of the two compounds from acetone solution,and subsequent heating until a melt formed followed by rapid cooling.Alternately, if the temperature of the solution is above that of themelting points of the individual acetylenic compounds, evaporation ofthe solution will lead directly to a melt.

A fifth process for preparing co-crystallized compounds of thisinvention comprises (a) vaporizing at least two acetylenic compounds and(b) depositing the resulting vapor onto a substrate.

In the vapor form, a mixture of the aceylenic compounds will be formed,which upon deposition will result in a co-crystallized composition.Converting the acetylenic compounds into the vapor form can beaccomplished in a number of conventional ways, but it is preferred tosublime the acetylenic compounds under reduced pressure by heating.Suitable substrates are discussed above for the deposition.

Devices for measuring temperature, comprising thermochromicco-crystallized compositions of this invention, and devices formeasuring time-temperature and radiation-dosage history comprisingco-crystallized compositions can be utilized for commercial articles.

A device for measuring temperature is also a subject of the inventioncomprising a substrate having deposited thereon at least onethermochromic co-crystallized composition of this invention. Athermochromic co-crystallized composition can be selected exhibiting acontrasting color change in the temperature region of interest and willreproducibly exhibit this color change through many heating and coolingcycles. Any suitable substrates may be chosen such as cardboard, filterpaper, flexible polymers, such as polyethylene, polypropylene and thelike, which choice will be obvious to one skilled in the art for asuitable application.

Further provided is a device comprising a series of thermochromicco-crystallized compositions, deposited on a substrate, each of whichhas a progressively higher thermochromic transition temperature than theprior composition in the series.

A device for measuring time-temperature or radiation-dosage history ofan article is also a subject of this invention and comprises a substratehaving deposited thereon a co-crystallized composition of this inventionwhich undergoes an irreversible color change upon exposure to thermalannealing or radiation, in which the hue and intensity of developedcolor are an integrated history of such exposure which can be determinedby reference to a suitable standard.

A specific embodiment of the device for measuring time-temperature orirradiation-dosage history of an article comprises a series ofco-crystallized acetylenic compounds in which the reactivity, i.e. therate of color development, the rate of undergoing a contracting colorchange, upon thermal annealing or exposing to actinic radiation, of eachcomposition in the series is greater to a known extent than the priorcomposition in the series. Thus, upon thermal annealing or exposing toactinic radiation, an integrated time-temperature or radiation-dosagehistory of the exposure time will be represented by the developed colorsof the individual compositions. The difference in reactivity of eachco-crystallized composition is achieved by varying the weight ratio ofthe composite acetylenic compounds comprising the composition. FIG. 4illustrates a general device of this type wherein a series ofco-crystallized compositions containing different weight ratios ofHDDPU/HDDPBPU exhibit different rates of color development upon thermalannealing at 80° C.

Commercial articles are stored in different types of containers such asmetal cans, glass bottles, plastic bags or bottles and paper orcardboard bags or boxes. The co-crystallized compositions of thisinvention as thermometer devices or time-temperature or radiation-dosagedevices can either be coated directly on the containers or can be coatedon paper or plastic and then applied, such as by pressure tape, to thecontainers. In either case a binder to bind the crystals of theco-crystallized compositions to the containers is required. In thepresent case we have used either shellac commonly available such as thatmade by Park Corporation, Somerset, Mass. or lacquer such as that madeby Zynolyte Products Company, Compton, Calif. or a binder. In someexamples no binder was used and the co-crystallized compositions werecoated directly on a substrate. Whatman filter papers (1) and aluminumfoils (2 to 10 mils thick) have been used as substrates. Theco-crystallized compositions were coated from solution either byspraying, spreading or brushing solution on a substrate. Thecompositions can also be coated by dipping the substrate in thesolution. Coating experiments can be easily used to obtain uniformcoatings of the co-crystallized compositions on a substrate.

Also a subject of this invention is a copolymeric composition comprisingan irradiated or thermally annealed product of a composition comprisedof at least two acetylenic compounds, each containing at least one--C.tbd.C--C.tbd.C-- groups, and substituents selected from the groupconsisting of sulfonate, urethane and alcohol radicals, at least one ofthe compounds capable of undergoing a contrasting color change uponexposure to actinic radiation or thermal annealing, wherein theco-crystallized composition exhibits a substantially differentthermogram than the sum of the individual components as obtained bydifferential scanning calorimetry.

Included among the copolymeric compositions are the co-crystallizedcompositions of this invention which have been thermally annealed orexposed to actinic radiation, such as gamma radiation, to form acopolymer which is useful in many polymer applications.

A specific embodiment of the copolymeric compositions is a shapedarticle, including a molded film, made from the copolymeric composition,wherein the decomposition temperature of the copolymeric composition isat least about 20° C. above the melting point of the composition.

This limitation is necessary to avoid degradation or charring of thecopolymeric composition upon compression or extrusion molding above itsmelting point under pressure. In general, the molding process is usuallyconducted at a temperature up to about 20° C. above the melting point,wherein no degradation of the copolymer occurs that would adverselyaffect quality of the molded product.

For example, the melting point of a copolymeric composition of 80/20weight percent of DDDECMU/4DECMU, i.e., 4,6-decadiyn-1,10-diolbis(ethoxycarbonylmethylurethane)/5,7-dodecadiyn-1,12-diolbis(ethoxycarbonylmethylurethane) produced by irradiating theco-crystallized composition with 50 Mrads, is 185°-195° C., and thedecomposition temperature is 230°-260° C., thus allowing the copolymericcomposition to be heat molded into shaped articles, including moldedfilms.

Representative examples of copolymeric compositions which can be meltedand shaped into articles or molded into films include 80/20 and 50/50weight percent compositions of DDDECMU/4DECMU, and 50/50 and 20/80weight percent compositions of DDDECMU/DDDBCMU, where DDDBCMU is4,6-decadiyn-1,10-diol bis(n-butoxycarbonylmethylurethane). Otherrepresentative examples are listed in Table VIII of Example 43.

In general, the copolymeric compositions are prepared by thermalannealing or irradiating a co-crystallized composition of thisinvention, with actinic radiation, preferably gamma radiation of adosage of about 50 Mrads and then treating with solvent to extractunreacted monomer. The copolymeric composition is then subjected toconventional molding techniques to produce a shaped article, preferablya molded film, which is useful in packaging and protective surfaceapplications.

Thermal Reactivity EXAMPLE 1

This example illustrates an increase in thermal reactivity byco-crystallization of 2,4-hexadiyn-1,6-diol bis(phenylurethane) (HDDPU)and 2,4-hexadiyn-1,6-diol bis(p-bromophenylurethane) (HDDPBPU).

TABLE 1 lists solutions of HDDPU and HDDPBPU which were prepared in 20ml. of acetone with 4 ml of lacquer added as a binder:

                  TABLE I                                                         ______________________________________                                        Solution   Weight of     Weight of                                            No.        HDDPU,g.      HDDPBPU,g.                                           ______________________________________                                        1          2             --                                                   2          1.99          0.01                                                 3          1.98          0.02                                                 4          1.96          0.04                                                 5          1.94          0.06                                                 6          1.90          0.10                                                 7          1.80          0.20                                                 8          1.60          0.40                                                 9          1.40          0.60                                                 10         1.20          0.80                                                 ______________________________________                                    

Each solution was then sprayed over a Whatman filter paper number 1 (9inch by 9 inch). The filter papers were first dried by dry nitrogen flowand then under vacuum. The drying process took about three minutes. Thefilter papers were then cut into 1 square inch pieces and stored at -20°C. The pieces of the filter paper were annealed at 80° C. for differentperiods of time. After annealing, the filter paper pieces were mountedaccording to their annealing time and concentration (proportion) ofHDDPU to form as array as depicted in FIG. 4. A graph is shown in FIG. 3for an annealing temperature of 80° C., in which the required time toturn metallic (end-point) in reciprocal hours is plotted versusconcentration of HDDPBPU in the composition. It is apparent from theFIG. 3 that the thermal reactivity of HDDPU is increased byco-crystallizing with HDDPBPU. The reactivity is maximum between 10 and20 percent of HDDPBPU, and the same effect was observed withco-crystallized compositions of HDDPU and 2,4 -hexadiyn-1,6-diolbis(p-chlorophenylurethane) (HDDPCPU).

EXAMPLE 2

This example illustrates a decrease in thermal reactivity byco-crystallization of 2,4-hexadiyn-1,6-diol bis(p-toluenesulfonate)(HDDPTS), and 3,5-octadiyn-1,8-diol bis(p-toluenesulfonate) (ODDPTS),for use in time-temperature indicators.

HDDPTS is thermally polymerizable while ODDPTS is not. Table II listscompositions of HDDPTS and ODDPTS were prepared in 12 ml of chloroformplus 3 ml of acetone; 3 ml of lacquer was added to each solution as abinder: 100% by weight of HDDPTS; 9:1 by weight of HDDPTS/ODDPTS; 8:2 byweight of HDDPTS/ODDPTS; and 7:3 by weight of HDDPTS/ODDPTS.

                  TABLE II                                                        ______________________________________                                        Approximate Time (hrs) Required to Turn Metallic                              at Different Relative Temperatures                                                       Temperature                                                        Composition  40° C.                                                                         50° C.                                                                         60° C.                                                                       70° C.                                                                       80° C.                        ______________________________________                                        100% HDDPTS  265      89     25    15    10                                   9:1                                                                           HDDPTS/ODDPTS                                                                              400     114     35    20    10                                   8:2                                                                           HDDPTS/ODDPTS                                                                              --      265     64    25    10                                   7:3                                                                           HDDPTS/ODDPTS                                                                              --      400     89    50    --                                   ______________________________________                                    

Each solution was sprayed over an aluminum foil (9 inch by 9 inch). Thecoating was first dried by dry nitrogen and then under vacuum. The foilwas then cut into 1 square inch pieces and annealed at approximately40°, 50°, 60°, 70° and 80° C. for 1, 2, 5, 10, 15, 25, 35, 45, 64, 89,114, 139, 164, 216, 265 and 400 hrs. The annealed pieces were thenmounted on sticky paper according to time and temperature for eachconcentration. The time required for the co-crystallized acetyleniccompounds to go metallic from red was estimated and the data aretabulated in the above Table. As can be seen from the Table, for a givenrelative temperature, the time required for the co-crystallizedacetylenic compounds to go metallic increased with increasingconcentration of ODDPTS. The estimated time required for HDDPTS alone togo metallic from red was about 3 to 4 months at room temperature (25°C.). Upon co-crystallization of HDDPTS with ODDPTS (30 percent byweight) the time required for the co-crystallized material to gometallic at room temperature was increased to about 12 to 15 months.

EXAMPLES 3-29 CO-CRYSTALLIZED ACETYLENIC COMPOUNDS

The following pairs of acetylenic compounds were co-crystallized andtested and found useful as time-temperature indicators:

    ______________________________________                                        Example                                                                              Pairs of Co-crystallized                                               No.    Acetylenic Compounds                                                   ______________________________________                                        3      2,4-hexadiyn-1,6-diol bis(n-butylurethane)                                    plus 2,4-hexadiyn-1,6-diol bis(ethylurethane)                          4      2,4-hexadiyn-1,6-diol bis(p-bromophenylurethane)                              and 2,4-hexadiyn-1,6-diol bis(p-chlorophenyl-                                 urethane)                                                              5      2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)                             plus 2,4-hexadiyn-1,6-diol bis(o-chlorophenyl-                                urethane)                                                              6      2,4-hexadiyn-1,6-diol bis(p-methoxyphenylurethane)                            plus 2,4-hexadiyn-1,6-diol bis(m-methoxyphenyl-                               urethane)                                                              7      2,4-hexadiyn-1,6-diol bis(o-tolylurethane) plus                               2,4-hexadiyn-1,6-diol bis(m-tolylurethane) -8 2,4-hexadiyn-1,6-diol            bis(n-hexylurethane) plus                                                    2,4-hexadiyn-1,6-diol bis(n-butylurethane)                             9      2,4-hexadiyn-1,6-diol bis(m-tolylurethane) plus                               2,4-hexadiyn-1,6-diol bis(p-tolylurethane) -10 2,4-hexadiyn-1,6-dio           l bis(o-tolylurethane) plus                                                   2,4-hexadiyn-1,6-diol bis(p-tolylurethane)                             11     2,4-hexadiyn-1,6-diol bis(m-chlorophenylurethane)                             plus 2,4-hexadiyn-1,6-diol bis(o-chlorophenyl-                                urethane)                                                              12     2,4-hexadiyn-1,6-diol bis(p-tolylurethane) plus                               2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)                      13     2,4-hexadiyn-1,6-diol bis(p-methoxyphenylurethane)                            plus 2,4-hexadiyn-1,6-diol bis(p-chlorophenyl-                                urethane)                                                              14     2,4-hexadiyn-1,6-diol bis(phenylurethane) plus                                2,4-hexadiyn-1,6-diol bis(m-chlorophenylurethane)                      15     2,4-hexadiyn-1,6-diol bis(phenylurethane) plus                                2,4-hexadiyn-1,6-diol bis(p-methoxyphenylurethane)                     16     2,4-hexadiyn-1,6-diol bis(phenylurethane) plus                                2,4-hexadiyn-1,6-diol bis(p-ethoxyphenylurethane)                      17     2,4-hexadiyn-1,6-diol bis(phenylurethane) plus                                2,4-hexadiyn-1,6-diol bis(o-chlorophenylurethane)                      18     3,5-octadiyn-1,8-diol bis(p-chlorophenylurethane)                             plus 3,5-octadiyn-1,8-diol bis(m-chlorophenyl-                                urethane)                                                              19     3,5-octadiyn-1,8-diol bis(m-tolylurethane) plus                               3,5-octadiyn-1,8-diol bis(o-tolylurethane)                             20     4,6-decadiyn-1,10-diol bis(butoxycarbonylmethyl-                              urethane) plus 4,6-decadiyn-1,10-diol bis(ethoxy-                             carbonylmethylurethane)                                                21     5,7-dodecadiyn-1,12-diol bis(o-tolylurethane)                                 plus 5,7-dodecadiyn-1,12-diol bis(m-tolylurethane)                     22     5,7-dodecadiyn-1,12-diol bis(p-chlorophenylurethane)                          plus 5,7-dodecadiyn-1,12-diol bis(p-bromophenyl-                              urethane)                                                              23     2,4-hexadiyn-1,6-diol bis(p-ethoxyphenylurethane)                             plus 3,5-octadiyn-1,8-diol bis(p-ethoxyphenyl-                                urethane)                                                              24     2,4-hexadiyn-1,6-diol bis(m-tolylurethane) plus                               3,5-octadiyn-1,8-diol bis(m-tolylurethane)                             25     2,4-hexadiyn-1,6-diol bis(n-hexylurethane) plus                               3,5-octadiyn-1,8-diol bis(n-hexylurethane)                             26     2,4-hexadiyn-1,6-diol bis(m-chlorophenylurethane)                             plus 3,5-octadiyn-1,8-diol bis(m-chlorophenyl-                                urethane)                                                              27     2,4-hexadiyn-1,6-diol bis(n-butylurethane) plus                               5,7-dodecadiyn-1,12-diol bis(n-butylurethane)                          28     4,6-decadiyn-1,10-diol bis(n-butylurethane) plus                              5,7-dodecadiyn-1,12-diol bis(n-butylurethane)                          29     3,5-octadiyn-1,6-diol plus 4,6-decadiyn-1,10-diol                      ______________________________________                                    

EXAMPLE 30

Some acetylenic compounds which upon co-crystallization do not show anythermal reactivity (or very little thermal reactivity) are stillpolymerizable by high energy radiation and can be used as radiationdosage indicators. The following are examples.

Co-crystallization of 2,4-hexadiyn-1,6-diol bis(m-chlorophenylurethane)(HDDMCPU) and 2,4-hexadiyn-1,6-diol bis(phenylurethane) (HDDPU) for useas radiation dosage indicators.

TABLE III lists solutions of HDDMCPU and HDDPU which were prepared in 10ml of tetrahydrofuran; 2 ml of commercial shellac was added as a binder.

                  TABLE III                                                       ______________________________________                                        Weight of HDDMCPU,g.                                                                             Weight of HDDPU,g.                                         ______________________________________                                        1.0                --                                                         0.9                0.1                                                        0.8                0.2                                                        0.7                0.3                                                        0.6                0.4                                                        0.5                0.5                                                        0.4                0.6                                                        0.3                0.7                                                        0.2                0.8                                                        0.1                0.9                                                        --                 1.0                                                        ______________________________________                                    

Each solution was sprayed on a 6 inch by 6 inch square of aluminum foil.The coating was dried under a stream of nitrogen followed byvacuum-drying for 24 hours. The co-crystallized HDDMCPU and HDDPU werenot thermally polymerizable prior to irradiation. The squares ofaluminum foil were then cut into 1 inch by 1 inch pieces and irradiatedwith Co⁶⁰ γ-rays at room temperature in air for dosages of 1, 2, 3, 4,5, 6, 7, 8, 9 and 10 Mrads. The dose required for the co-crystallizedacetylenic compounds turn to dark (dark violet) is shown in thefollowing Table IV.

                  TABLE IV                                                        ______________________________________                                        Proportion of                                                                             Dose Required to                                                  HDDMCPU,%   go Dark, Mrads                                                                              Comment                                             ______________________________________                                        100         7-8           --                                                  90          3             --                                                  80          2             --                                                  70          --            unreactive (pale                                                              yellow color)                                       60          --            unreactive (pale                                                              yellow color)                                       50          4             --                                                  40          less than 1   turns almost black                                  30          2             --                                                  20          4             --                                                  10          2             --                                                  0           3             --                                                  ______________________________________                                    

EXAMPLE 31

Co-crystallization of 2,4-hexadiyn-1,6-diol bis(phenylurethane) (HDDPU)and 3,5-octadiyn-1,8-diol bis(phenylurethane) (ODDPU) for use asradiation dosage indicators.

Table V lists solutions of HDDPU and ODDPU which were prepared in 10 mlof tetrahydrofuran; 2 ml of commercial lacquer was added as a binder.Each solution was sprayed on a 6 inch by 6 inch square of Number 1Whatman filter paper was preprinted with numerals 111--, 22213 , and thelike.

                  TABLE V                                                         ______________________________________                                        Weight of HDDPU,g.                                                                              Weight of ODDPU,g.                                          ______________________________________                                        1.0               --                                                          0.9               0.1                                                         0.7               0.3                                                         0.5               0.5                                                         0.3               0.7                                                         0.1               0.9                                                         --                1.0                                                         ______________________________________                                    

The coating was dried under a nitrogen flow followed by vacuum-dryingfor 25 hrs at room temperature. The co-crystallized acetylenic compoundswere not thermally polymerizable prior to radiation, that is, they didnot show any coloration even after a month at room temperature. Thefilter paper was cut into narrow strips, each having a specific numberwhich was clearly visible after coating. The strips were then irradiatedwith Co⁶⁰ γ-rays at room temperature in air for dosages of 1, 2, 3, 4,5, 6, 7, 8, 9 and 10 Mrads. Upon irradiation the coating turned pink-redor dark violet in color. The dose required for the number printedunderneath to become invisible is shown in the following table.

                  TABLE VI                                                        ______________________________________                                                         Dose, Mrads Required                                                          for the Number to                                            Percent of HDDPU Become Invisible                                             ______________________________________                                        100              less than 1                                                  90               4                                                            70               1-2                                                          50               1                                                            30               4                                                            10               1-2                                                          0                2                                                            ______________________________________                                    

The results indicate that co-crystallized compositions containing 90 and30 weight percent HDDPU exhibit highly desirable radiation-dosagecharacteristics since they are able to measure a larger amount of gammaradiation.

EXAMPLES 32 TO 36

The following is a list of pairs of acetylenic compounds which wereco-crystallized and tested as radiation dosage indicators. The method ofstudy used in the following examples was the same as in Example 30.

    ______________________________________                                        Example                                                                              Co-crystallized Pairs                                                  ______________________________________                                        32     2,4-hexadiyn-1,6-diol bis(m-chlorophenylurethane),                            and 2,4-hexadiyn-1,6-diol bis(phenylurethane)                          33     2,4-hexadiyn-1,6-diol bis(p-ethoxyphenylurethane)                             plus 2,4-hexadiyn-1,6-diol bis(phenylurethane)                         34     2,4-hexadiyn-1,6-diol bis(p-tolylurethane) plus                               2,4-hexadiyn-1,6-diol bis(p-chlorophenylurethane)                      35     2,4-hexadiyn-1,6-diol bis(p-methoxyphenylurethane)                            plus 2,4-hexadiyn-1,6-diol bis(p-chlorophenyl-                                urethane)                                                              36     2,4-hexadiyn-1,6-diol bis(o-chlorophenylurethane)                             plus 2,4-hexadiyn-1,6-diol bis(phenylurethane)                         ______________________________________                                    

EXAMPLES 37 to 42: Thermochromic Co-crystallized Acetylenic Compounds

The pairs of acetylenic compounds shown in the following table weremixed and dissolved in 100 ml of tetrahydrofuran. The solvent wasevaporated out at about 60° C. under reduced pressure (about 10 mm) in arotary evaporator within about 10 minutes. The residual solvent wasremoved under high vacuum at room temperature for 48 hrs. Theco-crystallized acetylenic compounds were irradiated with Co⁶⁰ γ-rays atroom temperature in air for 50 Mrads. The copolymers were heatedgradually on a Fisher-John's melting point apparatus. The temperature atwhich copolymers showed a color transition metallic (black) color to redcolor is shown in the table. The results indicate that in general thethermochromic transition temperature usually varies with the weightpercent composition of the co-crystallized material. However, in somecases (Example 41) this variation is slight. The following designationsare used for the acetylenic compounds:

1. DDDECMU-4,6-decadiyn-1,10-diol bis(ethoxycarbonylmethylurethane).

2. DDDBCMU-4,6-decadiyn-1,10-diol bis(n-butoxycarbonylmethylurethane).

3. 4DECMU-5,7-dodecadiyn-1,12-diol bis(ethoxycarbonylmethylurethane).

4. 4DBCMU-5,7-dodecadiyn-1,12-diol bis(n-butoxycarbonylmethylurethane).

5. DDDOTU-4,6-decadiyn-1,10-diol bis(o-tolylurethane).

6. DDDMTU-4,6-decadiyn-1,10-diol bis(m-tolylurethane).

7. DDDPTU-4,6-decadiyn-1,10-diol bis(p-tolylurethane).

                  TABLE VII                                                       ______________________________________                                        Ex-                                                                           am-                                                                           ple                       Weight of the                                       No.            Composition                                                                              Diacetylenes, G                                     ______________________________________                                        37             DDDECMU    --   0.2  0.5  0.8  1.0                                  color     DDDBCMU    1.0  0.8  05   02   --                                   transition                                                                    tempera-                                                                      ture, °C.                                                              after                                                                         50 Mrads             185  167  163  --   195                             38             DDDECMU    --   0.2  0.5  0.8  1.0                                  color     4DECMU     1.0  0.8  0.5  0.2  --                                   transition                                                                    tempera-                                                                      ture, °C.,                                                             after                                                                         50 Mrads             135  188  183  185  197                             39             DDDBCMU    --   0.2  0.5  0.8  1.0                                  color     4DBCMU     1.0  0.8  0.5  0.2  --                                   transition                                                                    tempera-                                                                      ture, °C.,                                                             after                                                                         50 Mrads             112  174  168  --   185                             40             4DECMU     --   0.2  0.5  0.8  1.0                                  color     4DBCMU     1.0  0.8  0.5  0.2  --                                   transition                                                                    tempera-                                                                      ture, °C.,                                                             after                                                                         50 Mrads             105  110  115  120  135                             41             DDDOTU     100   80   50  20                                                                             0                                        color     DDDMTU     --    20   50   80  100                                  transition                                                                    tempera-                                                                      ture, °C.,         195- 195- 205- 195-                                 after                                                                         50 Mrads             --   205  205  210  197                             42             DDDMTU     100   80   50   20  --                                   color     DDDPTU     --    20   50   80  100                                  transition                                                                    tempera-                                                                      ture, °C.,         250- 265-                                           after                                                                         50 Mrads             195  255  270  280  --                              ______________________________________                                    

EXAMPLE 43: Molding of Copolymeric Acetylenic Compounds into Films

The following copolymeric pairs of acetylenic compounds listed in TableVIII were molded into thin films (about 5 mil thick) by the followingprocedure: two acetylenic compounds were dissolved in a solvent and thesolvent was rapidly evaporated to yield a co-crystallized compositionwhich was dried under reduced pressure; the resulting co-crystallizedcomposition was irradiated with 50 Mrads of gamma radiation at roomtemperature to form a copolymeric composition and then treated withsolvent to extract out unreacted monomer; the copolymeric compositionwas then molded at a temperature above its melting point by compressionmolding at a pressure of about 15 tons to produce films. The films werepliable and reasonably strong and can be used in packaging andprotective coating applications. Films made from thermochromiccopolymeric compositions can be used as temperature indicator devices.The acetylenic compounds were chosen such that the co-crystallizedcomposition upon irradiation formed a copolymeric composition in whichthe decomposition temperature was at least about 20° C. above themelting point temperature. For example, the copolymeric pair,DDDECMU/4DECMU in an 80/20 weight ratio of starting monomers, had amelting point of 185°-195° C., and a decomposition temperature of about230°-260° C.; the copolymeric pair, DDDBCMU/4DBCMU in a 50/50 weightratio of starting monomers, had a melting point of 170° to 175° C., anda decomposition temperature of about 222° to 240° C.

                                      TABLE VIII                                  __________________________________________________________________________                                          Color Transition Temperature Range              Original Con-                                                                        Molding         Color of the                                                                         °C.                              Copolymeric                                                                           centration of                                                                        Temperature                                                                          Color of Film After                                                                           During                                                                              Reversible Transition             Pair    Monomer %                                                                            °C.                                                                           the Film Transition                                                                           Heating                                                                             During Cooling                    __________________________________________________________________________    1. DDDECMU                                                                            80     200    green gold                                                                             red    150-160                                                                             145-140                            4DECMU 20                                                                    2. DDDECMU                                                                            50     200    black green gold                                                                       red    150-155                                                                             145-140                            4DECMU 50                                                                    3. DDDECMU                                                                            50     170    black green gold                                                                       red    140-150                                                                             135-120                            DDDBCMU                                                                              50                                                                    4. DDDECMU                                                                            20     180    black green gold                                                                       red    160-168                                                                             140-135                            DDDBCMU                                                                              80                                                                    5. DDDBCMU                                                                            50     170    green gold                                                                             red    175-180                                                                             150-140                            4DBCMU 50                                                                    6. DDDBCMU                                                                            20     180    black green gold                                                                       red    150-160                                                                             140-135                            4DBCMU 80                                                                    7. 4DECMU                                                                             80     140    red gold orang  80-95 70-50                              4DBCMU 20                                                                    8. 4DECMU                                                                             50     120    green gold (red)                                                                       orange 80-95 70-50                              4DBCMU 50                                                                    9. 4DECMU                                                                             20     120    green gold (red)                                                                       orange 80-95 70-50                              4DBCMU 80                                                                    __________________________________________________________________________

DIRECT SYNTHESIS OF CO-CRYSTALLIZING ACETYLENIC COMPOUNDS EXAMPLE 44

In a three-necked flask fitted with a magnetic stirrer, an additionalfunnel and a thermometer, 11.0 g (0.1 mol) of 2,4-hexadiyn-1,6-diol and300 ml of tetrahydrofuran were added. Also added was 1 g ofdi-t-butyl-tin-di-2-ethylhexanoate and 1 ml of triethylamine ascatalysts. A solution of 4.95 g (0.025 mol) of p-bromophenyl isocyanateand 26.8 g (0.225 mol) of phenyl isocyanate in 100 ml of tetrahydrofuranwas added dropwise from the addition funnel over a period of 1 hr. Thereaction was allowed to proceed for 1 hr. Hexane was added toprecipitate the mixture of the diacetylenes. The precipitate wasfiltered off quickly as it started turning pink and was redissolved in100 ml of acetone. The mixture was stable in the solution.

This solution is referred to as HDDPBPUPU (10) in Example 47 below.

EXAMPLE 45

In a three-necked flask fitted with a magnetic stirrer, an additionfunnel and a thermometer 11.0 g (0.1 mol) of 2,4-hexadiyn-1,6-diol and300 ml of tetrahydrofuran were added. Also added were 1 g ofdi-t-butyl-tin-di-2-ethylhexanoate and 1 ml of triethylamine ascatalysts. A solution of 9.9 g (0.05 mol) of p-bromophenyl isocyanateand 23.8 g (0.2 mol) of phenyl isocyanate in 100 ml of tetrahydrofuranwas added dropwise from the addition funnel over a period of 1 hr. Thereaction was allowed to proceed for 1 hr. Hexane was added toprecipitate the mixture of the diacetylenes. The precipitate wasfiltered off quickly and redissolved in 100 ml of acetone. The mixtureof acetylenic compounds was stable in the solution. The solution isreferred to as HDDPBPUPU (20) in Example 47.

EXAMPLE 46

In a three-necked flask fitted with a magnetic stirrer, an additionfunnel and a thermometer, 11.0 g (0.1 mol) of 2,4-hexadiyn-1,6-diol and300 ml of tetrahydrofuran were added. Also added were 1 g ofdi-t-butyl-tin-di-2-ethylhexanoate and 1 g of triethylamine ascatalysts. A solution of 14.85 g (0.075 mol) of p-bromophenyl isocyanateand 20.8 g (0.175 mol) of phenyl isocyanate in 100 ml of tetrahydrofuranwas added dropwise from the addition funnel over a period of 1 hr. Thereaction was allowed to proceed for 1 hr. Hexane was added toprecipitate the mixture of the diacetylenes. The precipitate wasfiltered off and redissolved in 100 ml of acetone. The mixture ofacetylenic compounds was stable in solution. This solution is referredto as HDDPBPUPU (30) in the following Example (Example 47).

EXAMPLE 47

The solutions, HDDPBPUPU (10), (20) and (30) described in Examples 44,45 and 46, respectively, were sprayed on Number 2 Whatman filter andsolvent was evaporated. The following were the color developments, atroom temperature, of the coated samples, for the indicated time.

    ______________________________________                                        Color of HDDPBPUPU                                                            Time  (10)         (20)         (30)                                          ______________________________________                                        10 min                                                                              pink         slightly pink                                                                              almost white                                   2 hrs                                                                              red (slightly                                                                              pink         slightly pink                                        violet                                                                 24 hrs                                                                              violet       reddish pink slightly pink                                 ______________________________________                                    

I claim:
 1. A copolymeric composition comprising an actinicallyirradiated or thermally annealed product of a composition comprised ofat least two co-crystallized acetylenic compounds, of different chemicalstructures, each containing at least one --C.tbd.C--C.tbd.C-- group andsubstituents selected from the group consisting of sulfonate, urethane,and alcohol radicals, at least one of the compounds capable ofundergoing a contrasting color change upon exposure to actinic radiationor thermal annealing, wherein the composition exhibits a substantiallydifferent thermogram than the sum of thermograms of the individualcompounds as obtained by differential scanning calorimetry, and whereinthe composition exhibits a higher or lower rate of color change uponexposure to actinic radiation or thermal annealing than the individualcompounds.
 2. The composition of claim 1 wherein the copolymericcomposition possesses a decomposition temperature of at least about 20°C. above its melting point.
 3. A shaped article produced from thecomposition of claim
 2. 4. The article of claim 3 as a molded film.